Sulfenylated cycloalkylphenyl-n-methylcarbamates

ABSTRACT

SULFENYLATED CYCLOALKYLPHENYL-N-METHYLCARBAMATES OF THE GENERAL FORMULA   ((X-)3-C-S-N(-CH3)-COO-),(R)M,(R&#39;&#39;)N-BENZENE   IN WHICH R IS CYCLOALKYL WITH 5 TO 7 RING CARBON ATOMS OPTIONALLY SUBSTITUTED WITH 1 OR 2 ALKYL GROUPS R&#39;&#39; IS LOWER ALKYL OR ALKOXY, HALOGEN OR NITRO, X IS FLUORINE, CHLORINE OR BROMINE, M IS 1, 2 OR 3, AND N IS O, 1 OR 2, WHICH POSSESS INSECTICITAL, ACARICIDAL AND FUNGICIDAL PROPERTIES.

United States Patent US. Cl. 260-479 C 7 Claims ABSTRACT OF THE DISCLOSURE Sulfenylated cycloalkylphenyl-N-methylcarbamates of the general formula in which R is cycloalkyl with to 7 ring carbon atoms optionally substituted with 1 or 2 alkyl groups, R is lower alkyl or alkoxy, halogen or nitro, X is fluorine, chlorine or bromine, m is 1, 2 or 3, and n is 0, 1 or 2,

which possess insecticidal, acaricidal and fungicidal properties.

The present invention relates to and has for its objects the provision of particular new sulfenylated cycloalkylphenyl-N-methylcarbamates, i.e. (optionally alkyl-substituted mono-, di or tri-cycloalkyloptionally substituted-phenyl N methyl N trihalomethylrnercapto-carbamates, which possess insecticidal, acaricidal and fungicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids and fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification No. 1,159,938 that 2-cyclopentylphenyl-N-methylcarbamate (Company A) exhibits insecticidal activity.

The present invention provides, as new compounds, the N-sulfenylated cycloalkylphenyl N methylcarbamates of the general formula in which R is cycloalkyl with 5 to 7 ring carbon atoms optionally substituted with l or 2 alkyl groups, R is lower alkyl or alkoxy, halogen or nitro, X is fluorine, chlorine or bromine,

m is 1, 2 or 3, and nis 0, 1 or 2.

These new compounds are distinguished by strong insecticidal, acaricidal and fungicidal properties.

The present invention also provides a process for the preparation of a sulfenylated cycloalkylphenyl-N-methylcarbamate of the formula (I) above, in which an N-sulfenylated N-methyl-carbamic acid fluoride of the general formula -OX= is reacted with a cycloalkylphenol of the general formula )m (Rh (III) optionally in the presence of a diluent and optionally in the presence of an acid acceptor, in which formulas R, R, X, m and n have the meanings stated above.

It is decidely surprising that the compounds according to the invention exhibit a higher insecticidal, acaricidal and fungicidal potency than the known 2-cyclopentylphenyl-N- methylcarbamate. The compounds according to the invention therefore represent an enrichment of the art.

If 2-cyclopentylphenol and N-(fluorodichloromethylthio)-N-methylcarbamic acid fluoride are used as starting materials, the reaction course can be represented by the following equation:

| C O F I acid-bindlng H N-CH:

g agent (E C12 F (Illa) E(IIa) a O C O --N l g LQQ an The cycloalkylphenols to be used for the reaction are known and are defined by the formula (III). In this formula, as in formula (I), R is preferably cyclopentyl or 'cyclohexyl, either of which may be substituted by l or 2 lower alkyl groups, preferably containing 1 to 3 carbon atoms and especially methyl. R is preferably nitro, chlorine, bromine, or lower alkyl with 1 to 3 and preferably 1 or 2 carbon atoms, especially methyl.

As examples of the phenols which can be used as starting materials, there may be mentioned:

3 2-cyclopentyl-4-methylphenol, 2-cyclopentyl-S-methylphenol, 2-cyclopenty1-4,G-dimethylphenol, 3-cyclopentyl-4,6-dimethylphenol, 2,4-dicyclopentyl-S-methylphenol, 2,5-dicyclopentyl-4-methylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,4,S-tricyclopentylphenol, 2-cyclohexyl-4-methylphenol, 2-cyclohexyl-S-methylphenol, 2-cyclohexyl-4,6-dimethylphenol, 3-cyclohexyl-4,6-dimethylphenol, 2,4-dicyclohexyl-S-methylphenol, 2,S-dicyclohexyl-4-methylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,4,S-tricyclohexylphenol, 2-cyclopentyl-6-chlorophenol, 3-cyclopentyl-4-chlorophenol, 2-cyclohexyl-6-chlorophenol, 2-cyclohexyl-6-bromophenol, 3-cyclohexyl-4-chlorophenol, 2-cyclopentyl-4-nitrophenol, 2-cyclohexyl-4-nitrophenol, and the like.

The N-sulfenylated N-methylcarbamic acid fluorides to be used for the reaction are known and are defined by the formula (II). As shown in Belgian Patent Specification N. 717,705, they are obtainable from N-methylcarbamic acid fluoride and the appropriate sulfenyl chlorides, also described in the literature, in the presence of a tertiary amine.

Preparation of the compounds of this invention is effected preferably in the presence of a solvent or diluent. When working with solvents, those solvents are Preferably used which do not react, or reach only very slowly, with the N-sulfenylated N-methylcarbamic acid fluorides. As such solvents, there may be mentioned, for example, optionally chlorinated hydrocarbons such as benzene, toluene, methylene chloride, dichloroethane, chloroform, chlorobenzene and dichlorobenzene; and ethers, such as diethyl ether, tetrahydrofurane and dioxane. Mixture of such solvents are also suitable.

To bind the hydrogen fluoride formed during the reaction, an acid acceptor, preferably a tertiary base such as triethylamine or an inorganic base such as an alkali metal hydroxide or an alkali metal carbonate, is added to the reaction mixture. It is also possible to start directly from the corresponding alkali metal phenolate and carry out the reaction in aqueous phase.

The reaction temperatures can be varied within a fairly wide range. In general, the work is carried out at from about to 100 C., preferably at from to 40 C.

Usually, the reactants are used in approximately equimolar amounts.

The active compounds according to the invention exhibit strong insecticidal and acaricidal properties with low phytotoxicity. The active compounds can therefore be used with good results for the control of noxious sucking and biting insects, Diptera and mites (Acarimz). The compounds also exhibit a strong fungicidal activity, especially against soil borne and seed-borne fungal diseases of plants.

For these reasons, the compounds may be used in the crop-protection field, as well as in the hygiene field, as insecticides, acaricides and fungicides.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korscheltz'), the rosy apple aphid (Sappaphz's mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (T riatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (T ortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kathniella) and greater wax moth (Galleria mellonella) and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomentosus), the bean Weevil (Bruchidus=Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegabium paniceum), the yellow mealworm (T enebrio molitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Maderia cockroach (Leucophaea or Rhyparobia madeirae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the 'black blow fly (Phormia aegina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acari) contemplated herein there are classed, in particular, the spider mites (Terranychidae) such as the two-spotted spider mite (Tetranychus telarius= Tetranychus althaea or Tetranychus urticae) and the European red mite (Paratetranychus pil0sus=Pan0nychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the compounds of the invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray'powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/ or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), parafiins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, and fungicides, or bactericides, nematocides, herbicides, rodenticides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 0.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.001-l0%, preferably 0.014%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is eifective for the purpose in question and which is generally between about 0.00l%, and preferably 0.01-95 by weight of the mixture.

The active compounds can also be used in accordance with the well-known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g./hectare, preferably 40 to 600 g./hectare, are sufiicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids and fungi, and more particularly methods of combating at least one of insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (c) such fungi, and (d) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally or fungicidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforemnetioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 24 g. of 2-cyclopentylphenol (0.15 mole) and 31.5 g. of N-(fluorodichloromethylmercapto)-N-methyl-carbamic acid fluoride (0.15 mole) are dissolved in 200 ml. of dioxane. To this solution there are added dropwise, at room temperutare, 15 g. of triethylamine dissolved in 20 ml. of dioxane. After subsidence of the mildly exothermic reaction, stirring is effected for 1 hour at room temperature, then for 30 minutes at 50 to 60 C., followed by cooling; the reaction solution is then poured into 500 ml. of icewater. The oil obtained is taken up in methylene chloride and washed with water. After drying of the solution and evaporation of the methylene chloride, there are methyl-N-dichlorofiuoromethylmercapto-carbamate 7 as a yellowish-colored oil; b.p. 151 to 153 C./0.15 mm. Hg.

Analysis.Calc. (percent): C, 47.8; H, 4.6; 'CI, 20.1; N, 4.0; S, 9.1. Found (percent): C, 47.6; H, 4.9; Cl, 19.7; N, 4.2; S, 9.2.

In an analogous manner to that described above, the 5 following compounds are obtained 8 Analysis.Calcd. (percent): C, 49.1; H, 4.9; CI, 19.4; 3.8; S, 8.8. Found (percent): C, 48.1; H, 4.9; CI, 19.7; 4.2; S, 9.2.

EXAMPLE 3 In an analogous manner to that described in Example 2,

2 cyclopentyl-4-methyl-phenyl N-methyl-N-dichlorofiuo- ()C ONS C 013 (4) lCH (|)C ONS-C F3 0-0 ONS 0 C1:

(|)C ONS-C ClFI (|)C ONS-C F! EXAMPLE 2 To a sodium-2-cyclohexylphenolate solution, which was prepared from 26 g. of 2-cyclohexylphenol (0.15 mole), 65

B.P.: 192 to 195 010.4

mm. Hg.

B.P.: 11318 to 140 C./0.2

B.P.: 128 to 130 C.I0.22

mm. H.

Oil: no" 1.5526! B.P.: 153 to 155 C./0.21

mm. Hg.

B.P.: 138 to 140 C./0.22

mm. Hg.

romethylmercapto-carbamate of the following formula is obtained:

The pesticidal effectiveness of the compounds of the 75 present invention is illustrated in and by the following Examples, in which the active compounds of this invention are identified by the numbers assigned to them in the foregoing preparative Examples.

EXAMPLE 4 LT test for Diptera Test animals: Musca domestica Solvent: acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely 1: evaporated. The amount of active compound per square TABLE 1 L'Imo test for dipters Concentration of active compound of the solution Active compounds in percent Llw (A) O-CO-NHCH; 1.0 6 =85% (known) B 1.0 8 =07 o-oo-NHoH,

(known) 1 OH: 1.0 U l 0.2

fiJ-CO-N-S-CClzF 0.04 6

l 0.2 e =9o% 0-0 O-NS-C Ch CH 1.0 30' (3) I a 0.2 30 0C0-N-SCC1F1 0.04 I3 CH 1.0 30' (4) I i 0.2 30 OC0-NSCF| 0.04 75 CH 1.0 75' (6) 0.2 s

OCONSCC1F: 0.04 6=20% TABLE 1Continued Concentration oiaetiva compound the solution Active compounds in percent LTm 0.2 105' ()--CON--SCF; 0,04 8h H l 0.2 6 (|)CONSCC1:F

EXAMPLE The Petri dish remains uncovered until the solvent has bDmo test completely evaporated. The amount of active compound per square meter of filter paper varies with the concen- Test ammals: Tnatoma mfestans'hd nymphal Stage tration of the solution of active compound used. 15 test Solvent: acetone animals are then placed in the Petri dish and it is covered I 2 parts by weight of the active compound are dissolved With a g s in 1000 parts by volume of the solvent. The solution so The cohdltloh 0f the test 'ahlmalstls Observed 3 y obtained is diluted with further solvent to the desired concomlhehcemeht 0f the expel'lmehls- The dstl'llccentrations, tron 1s deterrmned as a percentage.

2.5 ml. of the solution of the active compound are The active compounds, the concentrations of the active pipetted into a Petri dish. On the bottom of the Petri dish compounds and the results can be seen from the followthere is 'a filter paper with a diameter of about 9.5 cm. ing Table 2:

TABLE 2 LDioo test Concentration of active compound 01 Destructhe solution tion in Active compounds in percent percent (A) BO-C O-NHCIL 1. 0

(known) 0-0 O-NHCH: H I

(known) (1) CHI 1. 0 0. 2 100 00 O-N-SC ClzF 0. M 100 D (2).--. CH; 1.0 100 i 0. 2 100 0-0 O-N-S-CCI; 0.04 80 TABLE 2Contlnued i h concelgtvcttifx compound of Destructhe solution tionin Active compounds in percent percent (3) 1 CH3 l 1.0 100 I 0.2 100 (|)C O-N-S-CCIF, V v 0.04 no (4) CE: 1.0 100 0.2 100 o-c O-NSC F; 04

7 CH| 1.0 100 0.2 100 (J-C 0--NSC F,

EXAMPLE 6 80 The Petri dish remains uncovered until the solvent has D test completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. test animals are then placed in the Petri dish and it is covered 2 parts by weight of the active compound are dissolved W a glass in 1000 parts by volume of the'solvent. The solution so, The condition of the test animals is Observed 3 y obtained is diluted with further solvent to the desired after the cOmmencemcht of the experiments- The destrucconcentrations. tion is determined as a percentage.

2.5 ml. of the solution of the active compound are 40 The active compounds, the concentrations of the active pipetted into a Petri dish. On the bottom of the Petri'dish compounds and the results can be seen from the followthere isa filter paper with a diameter of about 9.5 'cm. ing Table 3:

Test animals: Trib'olium confusum Solvent: Acetone TABLE 3Continued Qoncentration elective compound of Destructhe solution tion in Active compounds in percent percent;

0.2 100 O-C O-N-S-C 01F; 0. 04 60 i (4) CH; 1.0 100 l 0.2 100 -0 O-NS-C F; 0. 04 100 0.008 li (6) CH; 1.0 100 0.2 100 0-0 O-N--SC CIF: 0. 04 :I

(7) CH; 1.0 100 0.2 100 (l)C O-N-S-CF; 0. 04 50 EXAMPLE 7 r tained is diluted with-water to the desired lower concen- Mosquito larvae test Emulsifier: 1 part by weight benzylhydroxydipheuyl polyglycol ether To produce a suitable preparation of active compound, 2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent containing the trations. i v The aqueous preparations of the active compounds are placed iruglass vessels and about 25 mosquito larvae are thenplaced'in eachl glass vessel. v

After 24 hours, thedegree of destruction is determined as a percentage. means that all the larvae are killed. 0% means that no larvae at all are killed.

The active compounds, the concentrations of the active compounds, the test animals and the results can be seen amount of emulsifier stated above. The solution thus obfrom Table 4:

TABLE 4 Mosquito larvae test Concentration of active Degree of compound of destructhe solution tion in Active compound in percent percent (A); O-C O-NHCH; 10 100 H I 1 0 (known) 0-0 0--NHCH:

" meme 1 :.1 CH 10 100 a 1 100 0-0 O--NS C 01;]? 0.1 30

. 17 1 8 new Hontinued i I l l l V Concentration ottiotive Degree of a l l compound destruc I the solution tion in Active compound 1 in percent percent 3 CH 100 a v 1 100 I -oo-N-s--cc1m 6 ..'.':;::::::r CH 10 10C w I I l I la) 0-C0-NSCC1F:

8 I there is a filter paper with a diameter of about 9.5 cm, The Petri dish remains uncovered suntil the solvent has LD tcst completely evaporated. The amount of active compound V persquare meter of filter paper vat'ies with the concentrai' g gfigmgfig gggg k 95 tionof the solution of active compound used. 15 test ani- Solventz' done mals are then placed in the Petri dish and it is covered with a glass lid. 2 parts y weight of the active compound are dlssolved The condition of the test animals is observed 3 days in 1000 parts by volume of the solvent. The solution-so 7 after the commencement of the experiments. The destrucobtained is diluted with further solvent to the desired tion is determined asapercentage. concentrations. Y i i The active compounds, the concentrations of the ac- 2.5' ml.- of the solution of the 1 active compound ere tive compounds, the test animals and the results can be pipetted into'a Petri' dish On the hottom' 0f the Petri,,'dish seen from the following Table 5:

TABLE 5 LDieotost Concentration i, n ofacflvacompoundoLDestructhe solution tlon in Active compounds in percent 'percent o-co-mrc 1.0 100 I H. 0.2 100 0.04 I so u} v to 0-6 Os-NHCHI on, 1.0 1' 0.2 400 0-C0-NB-OC1F 0.04 a so 4 .srszf'izzzzzx: CE 1.0 100 I 0.2 1(1) C0-.Ns-,-CF 0.04 v1U) 0.008 80 compound of Destruc the solution tion in Actlvecompounds I 1t in percent percent, if V H: kg

O-GO-N-S-CCIF: 0.04 100 EXAMPLE 9 Cabbage plants (Brassic ialera cea) which have been heavily infested with peach aphids (Myzus persicae) are Myzus test (contact action) sprayed with the preparation of the active compound until t.t d p w than. Ta. Solvent. 3 parts by weight dlmethyl formamrde 20 Aftr the specified periods of time, the degree of Emulslfier: 1 part by weight alkylarylpolyglycol ether struction is determined as a percentage: 100% means To produce a suitable preparation of active compound, that all the aphids are kill'edwhereas 0% means that none 1 part by weight of the active compound is mixed with fth hi am i11 I the stated amount of solvent containing the stated amount e active th -con t ti of the active 0f emulsifier and the Concentrate is ed .t hf t0 2 .compounds,,the evaluation ,times and. the results canbe the desired concenll'afioflseen from the following Table 6. 1

' Myzustest V Degree of 1' Concentration destruct. of active '4 tion in compound of percent the solution after Active compounds in percent 1 day (A) O-C O-NHCH 0. 2 98 H I 0.02 40 0.002 0 (known) 0-0 O-NHCH:

(known) TABLE 6-Continued Emulsifier; 1 part fiy wei ghtalky laryi polyglycol ether To produce asuitable preparation 0!: active compound, 1 part by weight of the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier and theconcentrate'so obtaiue is diluted with waterlto the' des'iredcor'icentration; v L U Beanplants (Phaseoliwvulgaris), which have a height of approximately 10-30 cm are sprayed with the prepall the spider mites are killed whereas 0% means that none of the spider mites are killed. v The activeconi funds, the concentrations o thiactr e' compounds, the evaluation times and thefis'ul't's' seen from .thetfollowing Table 7: v 1 '1 l ,V B LE 7 t yehus test/resistant Concentration Degree of of active destruccompound tion utter Active compoundsw inpercent "z days o-co-vnncm of act lve destruc- Concentration Degree of compound; t'ton after EXAMPLE 11 Mycelium growth test Nutrient medium used:

20 parts by weight agar-agar 200 parts by weight potato decoction parts by weight malt parts by weight dextrose 5 parts by weight peptome 2 parts by weight Na HPO 0.3 parts by weight Ca(NO Proportion of solvent mixture to nutrient medium:

in percent 2 days I 0.01 parts by weight emulsifier (benzylhydroxydiphenylpolyglycol ether) 1.80 parts by weight water The amount of active compound required for the desired concentration of active compound in the nutrient 2 parts by weight solvent mixture 100 parts by weight agar nutrient medium Composition of solvent mixture:

0.19 parts by weight dimethyl formamide It will be appreciated that the instant specification and examples are set forth by 'way of illustration and not limitation, and that various modifications and changes 7 may be made without departing from the spirit and scope 5 of the present invention.

H i What is claimed is: e I

1. N-sulfenylated cycloalkylphenylcarbamates of the general formula new a Mycelium growth test 25 Evaluation is carried out; after 4-10 days, depending The active compounds, the concentratitms of the active upon the speed of growth of the fungi When evaluation is carried out the radial growth of the myceliumvon the treated nutrient media is compared with the. -growth,on the control nutrient medium.v In theevaluation of the fungus growth, the following characteristic values are v used:

0 no fungus growth 1 very strong inhibition of growth 2 medium inhibition'of growth 3 slight inhibition of growth t 4 growth equal to that of untreated control.

compounds and the results can be seen from the tollowing Table 8: i

27 in which R is cyclopentyl or cyclohexyl optionally substituted with 1 or 2 lower alkyl groups, R' is lower alkyl, lower alkoxy, halogen or nitro, X is fluorine, chlorine or bromine, mis1,2or3,and ,7. nis0,10r2. 2. Compounds according to claim 1, in which the, or each R may be substituted by 1 or 2 C -C alkyl groups, and the or each R is alkyl with 1 or 2 carbon atoms, nitro, chlorine or bromine.

3. The compound according to claim 1 wherein such compound is 2-cyclopentyl-phenyl N-methyl-N-dichlorofluoro methylmercapto-carbamate of the formula 6. Thecompound according-to claim 1 whereinsuch compound is Z-cycIopentyl-phenyl N-methyl-N-trifiuoromethylmercapto-carbamate'of the formula 7. The compound according to claim 1 wherein such compound is 2-cyclohexyl-phenyl N-methyl-N-trifluoro- 4. The compound according to claim 1 wherein such compound is 2-cyclopentyl-phenyl N-methyl-N-trichloromethylmercapto-carbamate of the formula f methyl-mercapto-carbamate of the formula US. Cl. X.R.

m) v 1mg l'A'mm' 0M1 0 ERTIFICATE OF CORRECTION I Patent No 3,819,682 7 Datedv June 25, 1974 Inventor-(a) GERHARD AL It is certified that after appears- 1n the aboye-identified patent and that said Letters Patent are hereby corrected as shown below:

, Col. 1, line 53, cancel "Comfaany" and substitute Compound Col. 3, line 34; canoe]. "reach" amisubstitute react --'-a C01. 5, line 70, change 90.001 to 000001 C016 '6, line5, change '"0.001" to 0.0001

Col. 6, line. 66, correct spelling of "temperature".

Col. 25, in the Table, correct compound (1) "to read as follows:

3 Y o-co-n-s-ccl s 001.: 26, line l0,"c1aim 1, in the formula, change double bond to single bond 0 between C0 and N.

. Signed and sealed thisj29th day of Octoberl974.

' (SEAL) Attest:

I McCOY M. GIBSON-JR. c. ARssALL DANN Attesting Officer 1 Commissmner of Patents 

